The instant invention relates to an improved bleach process in the presence of a metal complex catalyst, hydrogen peroxide or a precursor of hydrogen peroxide and a carboxylic acid anhydride. Further aspects of the invention are the use of a metal complex catalyst together with hydrogen peroxide or a precursor of hydrogen peroxide and a carboxylic acid anhydride as a bleaching composition and specific formulations containing the bleaching composition.

Traditionally, peroxide-containing bleaching agents have been used in washing and cleaning processes. They have an excellent action at a liquor temperature of 90 ⁰ C and above, but their performance noticeably decreases with lower temperatures. Currently, peroxy acid precursors are used to activate peroxide-containing bleaching agents. Tetraacetyl ethylenediamine (TAED) is mainly used as the activator in European washing systems. US systems, on the other hand, are frequently based on sodium nonanoylbenzosulfonate (Na- NOBS). Activator systems are effective in general, but the bleaching action of currently customary activators is inadequate under certain but desirable washing conditions (e.g. low temperature, short wash cycle).

It is known that, in addition to bleach activators, some transition metal complexes are capable of activating hydrogen peroxide and thus accelerating bleaching processes.

In respect of H ₂ O ₂ activation having effective bleaching action, mononuclear and polynuclear variants of manganese complexes with various ligands, especially 1 ,4,7-trimethyl-1 ,4,7- triazacyclononane and optionally oxygen-containing bridge ligands, are currently regarded as being especially effective. Such catalysts have adequate stability under practical conditions and, with Mn ⁿ⁺ , contain an ecologically acceptable metal cation, but their use is unfortunately associated with considerable damage to dyes and fibres.

In the present invention, it has now, surprisingly, been found that terpyridine metal complexes are capable of acting as catalysts in bleaching reactions together with carboxylic acid anhydrides. The advantage of these combinations is that they can considerably enhance the bleach performance of present bleach systems that consist of H ₂ O ₂ and/or precursors of H ₂ O ₂ . Furthermore, because of their catalytic action, the performance increase can be obtained with only small amounts.

The invention accordingly relates to a process for the bleaching of stains or of soiling on textile material in the context of a washing process or by the direct application of a stain remover, which process comprises bringing into contact in an aqueous medium a) a fiber or fabric; b) a carboxylic anhydride and hydrogen peroxide or the precursor of hydrogen peroxide; c) a metal complex of formula (1 )

[L _n Me _m Xp]Υ _q (1 ),

wherein Me is manganese, titanium, iron, cobalt, nickel or copper,

X is a coordinating or bridging radical, n and m are each independently of the other an integer having a value of from 1 to 8, p is an integer having a value of from 0 to 32, z is the charge of the metal complex,

Y is a counter-ion, q = z/(charge Y), and

L is a ligand of formula (2)

wherein

Ri, R2, R3, R ₄ , Rs, Re, R ₇ , Rs, R9, R10 and Rn are each independently of the others hydrogen; unsubstituted or substituted Ci-Ci ₈ alkyl or aryl; cyano; halogen; nitro; - COORi ₂ or -SOsRi ₂ wherein Ri ₂ is in each case hydrogen, a cation or unsubstituted or substituted Ci-Ci ₈ alkyl or aryl; -SRi ₃ , -SO ₂ Ri ₃ or -ORi ₃ wherein Ri ₃ is in each case hydrogen or unsubstituted or substituted Ci-Ci ₈ alkyl or aryl; -NRi ₄ Ri ₅ ; -(Ci-C ₆ alkylene)-NR ₁₄ Ri ₅ ; -N ⁰ R ₁₄ Ri ₅ Ri ₆ ; -(Ci-C ₆ alkylene)-N ^Θ Ri ₄ Ri5Ri6; -N(Ri ₃ )-(Ci- C ₆ alkylene)-NRi ₄ Ri ₅ ; -N[(Ci-C ₆ alkylene)-NRi ₄ Ri5] ₂ ; -N(Ri ₃ )-(C _r C ₆ alkylene)-

N ⁰ Ri ₄ Ri ₅ Ri ₆ , -N[(Ci-C ₆ alkylene)-N ^Θ Ri ₄ Ri ₅ Ri ₆ ] ₂ ; -N(Ri ₃ )-N-Ri ₄ Ri ₅ or -N(Ri ₃ )- N ^Θ Ri ₄ Ri ₅ Ri6, wherein Ri ₃ is as defined above and Ri ₄ , Ri ₅ and Ri ₆ are each independ- ently of the other(s) hydrogen or unsubstituted or substituted Ci-Ci ₈ alkyl or aryl, or Ri ₄ and Ri ₅ together with the nitrogen atom bonding them form an unsubstituted or substituted 5-, 6- or 7-membered ring which may optionally contain further heteroatoms; or Ri, R ₂ , Rβ, R ₄ , R ₅ , R ₆ , R7, Re, R9, R10 and Rn are each independently of the others a group _ _{N NH} . _ _{N N} _ _CH2CH2θH . __ _{N N} _ _C H ₃ . — N N ^* _Ch| ³ ; and optionally d) a surfactant and further adjuvants.

The process is for example carried out in such a way that the pH-value at the end of the process is from 8 to 10.5, preferably from 8.5 to 10.

In general the process is carried out at a temperature from 4° C to 95°C at normal pressure.

The Ci-Ci ₈ alkyl radicals mentioned are generally, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl. Preference is given to Ci-Ci ₂ alkyl radicals, especially Ci-C ₈ alkyl radicals and preferably Ci-C ₄ alkyl radicals. The mentioned alkyl radicals can be unsubstituted or substituted e.g. by hydroxyl, Ci-C ₄ alkoxy, sulfo or by sulfato, especially by hydroxyl. The corresponding unsubstituted alkyl radicals are preferred. Very special preference is given to methyl and ethyl, especially methyl.

Examples of aryl radicals that generally come into consideration are phenyl or naphthyl unsubstituted or substituted by Ci-C ₄ alkyl, Ci-C ₄ alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino, N-mono- or N,N-di-Ci-C ₄ alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, where the amino groups may - A -

be quaternized, phenyl, phenoxy or by naphthoxy. Preferred substituents are CrC ₄ alkyl,

CrC ₄ alkoxy, phenyl and hydroxy.

Special preference is given to the corresponding phenyl radicals.

The Ci-C ₆ alkylene groups mentioned are generally, for example, straight-chain or branched alkylene radicals such as methylene, ethylene, n-propylene or n-butylene. The alkylene radicals mentioned can be unsubstituted or substituted, for example by hydroxyl or Ci-C ₄ alkoxy.

Halogen is generally preferably chlorine, bromine or fluorine, special preference being given to chlorine.

Examples of cations that generally come into consideration are alkali metal cations, such as lithium, potassium and especially sodium, alkaline earth metal cations, such as magnesium and calcium, and ammonium cations. The corresponding alkali metal cations, especially sodium, are preferred.

Suitable metal ions for Me are e.g. manganese in oxidation states N-V, titanium in oxidation states III and IV, iron in oxidation states I to IV, cobalt in oxidation states I to III, nickel in oxidation states I to III and copper in oxidation states I to III, with special preference being given to manganese, especially manganese in oxidation states Il to IV, preferably in oxidation state II. Also of interest are titanium IV, iron N-IV, cobalt N-III, nickel N-III and copper N-III, especially iron N-IV.

For example, Me is manganese which is present in oxidation state N, III, IV or V; or Fe in oxidation state II, III or IV.

Preferably Me is manganese which is present in oxidation state N, III, IV or V.

For the radical X there come into consideration, for example, CH ₃ CN, H ₂ O, F ^" , Cl ^" , Br ^" , HOO ^" , O ₂ ^2" , O ^2" , Ri ₇ COO ^" , R ₁ 7O ^" , LMeO ^" or LMeOO ^" wherein R ₁₇ is hydrogen, -SO ₃ C _r C ₄ alkyl, or unsubstituted or substituted Ci-Ci ₈ alkyl or aryl, and L and Me are as defined above. Ri ₇ is especially preferably hydrogen, Ci-C ₄ alkyl; sulfophenyl or phenyl, especially hydrogen. As counter-ion Y there come into consideration, for example, Ri ₇ COO ^" , CIO ₄ ^" , BF ₄ ^" , PF ₆ ^" , Ri ₇ SO ₃ ^" , Ri ₇ SO ₄ ^" , SO ₄ ^2" , NO ₃ ^" , F ^" , Cl ^" , Br ^" , I ^" , citrate, tartrate or oxalate wherein R ₁₇ is hydrogen or unsubstituted or substituted CrC ₁₈ alkyl or aryl. R ₁₇ as CrC ₁₈ alkyl or aryl has the definitions and preferred meanings given hereinabove and hereinbelow. R ₁₇ is especially preferably hydrogen, CrC ₄ alkyl; phenyl or sulfophenyl, especially hydrogen or 4-sulfophenyl. The charge of the counter-ion Y is accordingly preferably 1- or 2-, especially 1-. Y can also be a customary organic counter-ion, such as citrate, oxalate or tartrate.

For example, n is an integer having a value of from 1 to 4, preferably from 1 to 2.

For example, m is an integer having a value of 1 or 2, especially 1.

For example, p is an integer having a value of from 0 to 4, preferably from 0 to 2.

For example, z is an integer having a value of from 8- to 8+, preferably from 0 to 2+.

R ₁₂ is preferably hydrogen, a cation, CrC ₁₂ alkyl, or phenyl unsubstituted or substituted as indicated above. R ₁₂ is especially preferably hydrogen, an alkali metal cation, alkaline earth metal cation or ammonium cation, CrC ₄ alkyl or phenyl, more especially hydrogen or an alkali metal cation, alkaline earth metal cation or ammonium cation.

R ₁₃ is preferably hydrogen, CrC ₁₂ alkyl, or phenyl unsubstituted or substituted as indicated above. R ₁₃ is especially preferably hydrogen, CrC ₄ alkyl or phenyl, more especially hydrogen or C-ι-C ₄ alkyl, preferably hydrogen. Examples of the radical of the formula -OR ₁₃ that may be mentioned include hydroxyl and CrC ₄ alkoxy, such as methoxy and especially ethoxy.

When R ₁₄ and R ₁₅ together with the nitrogen atom bonding them form a 5-, 6- or 7-membered ring it is preferably an unsubstituted or CrC ₄ alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring, where the amino groups can optionally be quaternized, preferably the nitrogen atoms which are not directly bonded to one of the three pyridine rings A, B or C being quaternized. The piperazine ring can be substituted by one or two unsubstituted C-ι-C ₄ alkyl and/or substituted C-ι-C ₄ alkyl e.g. at the nitrogen atom not bonded to the phenyl radical. In addition, R ₁₄ , R ₁₅ and R ₁₆ are preferably hydrogen, unsubstituted or hydroxyl-substituted CrC ₁₂ alkyl, or phenyl unsubstituted or substituted as indicated above. Special preference is given to hydrogen, unsubstituted or hydroxyl- substituted Ci-C ₄ alkyl or phenyl, especially hydrogen or unsubstituted or hydroxyl-substituted Ci-C ₄ alkyl, preferably hydrogen.

Preference is given to compounds wherein the ligand L is a compound of formula (3)

wherein

R' ₃ , R' ₆ and R' ₉ are each independently of the others phenyl unsubstituted or substituted by

Ci-C ₄ alkyl, Ci-C ₄ alkoxy, halogen, phenyl or hydroxyl; cyano; nitro; -COORi ₂ or -SO ₃ Ri ₂ , wherein R ₁₂ is in each case hydrogen, a cation, Ci-C ₄ alkyl or phenyl; -SRi ₃ , -SO ₂ Ri ₃ or -ORi ₃ wherein Ri ₃ is in each case hydrogen, Ci-C ₄ alkyl or phenyl, -N(CH ₃ )-NH ₂ Or -NH-NH ₂ ; amino; N-mono- or N,N-di-Ci-C ₄ alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, may be quaternized; N-mono- or N,N-di-CrC ₄ alkyl- N ^Θ Ri ₄ Ri ₅ Ri6, unsubstituted or substituted by hydroxy in the alkyl moiety, wherein Ri ₄ , Ri ₅ and Ri ₆ are each independently of the others hydrogen, unsubstituted or hydroxyl-substituted Ci-Ci ₂ alkyl, or phenyl unsubstituted or substituted as indicated above, or Ri ₄ and Ri ₅ together with the nitrogen atom bonding them form a pyrrolidine, piperidine, morpholine or azepane ring unsubstituted or substituted by at least one Ci-C ₄ alkyl or by at least one unsubstituted CrC ₄ alkyl and/or substituted CrC ₄ alkyl wherein the nitrogen atom can be quaternized; N-mono- or N,N-di-Ci-C ₄ alkyl-NRi ₄ Ri ₅ unsubstituted or substituted by hydroxy in the alkyl moiety, wherein Ri ₄ and Ri ₅ can have the meanings indicated above; or a radical

- (CH ₂ ) ₀ — N N

^ ' ^R 18 wherein Ri ₇ and Ri ₈ are Ci-C ₄ alkyl or Ci-C ₄ alkyl substituted by OH; R ₃ ' and R ₉ ' can have additionally the meaning of hydrogen.

Especially important as radicals R ₆ and R ₆ ' are Ci-C ₄ alkoxy; hydroxy; hydrazine; amino; N-mono- or N,N-di-Ci-C ₄ alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms which are not bonded to one of the three pyridine rings A, B or C, may be quaternized; or a pyrrolidine, piperidine, piperazine, morpholine or azepane ring unsubstituted or substituted by at least one CrC ₄ alkyl, wherein the nitrogen atoms may be quaternized. A further especially important example of R ₆ is the radical

wherein the ring and the two alkyl groups may additionally be substituted.

Very especially important as radicals R ₆ and R ₆ ' are Ci-C ₄ alkoxy; hydroxy; N-mono- or N,N-di-Ci-C ₄ alkylamino substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms which are not bonded to one of the three pyridine rings A, B or C, may be quaternized; or a pyrrolidine, piperidine, morpholine or azepane ring unsubstituted or substituted by at least one Ci-C ₄ alkyl, wherein the amino groups may be quaternized.

A further very especially important example of R ₆ is the radical

wherein the ring and the two alkyl groups may additionally be substituted.

As examples of the radical R ₆ , particular mention may be made of

— N N ^■ — N N-CH ₀ CH ₀ OH ■ — N N-CH, ^■ — N N'

CH _Q

_V1-1 ^CH ₂ CH ₂ OH _V1+ ^CH ₂ CH ₂ OH

— N N- ■ — NCH ₂ CH ₂ N(CH ₃ ) ₃ -NCH ₂ CH ₂ N(CH ₃ ) ₂

CH _Q — N N.

CH ₂ CH ₂ OH ChL ChL

-NHCH ₂ CH ₂ N(CH ₃ ) _{3 ;} -NHCH ₂ CH ₂ N(CH ₃ ) _{2 ;} -N[CH ₂ CH ₂ N(CH ₃ ) ₃ ] ₂ -N[CH ₂ CH ₂ N(CH ₃ ) 2J2

-N[CH ₂ CH ₂ CH ₂ N(CH ₃ ) ₂ ] ₂ and -N[CH ₂ CH ₂ CH ₂ N(CH ₃ ) ₃ ] ₂ . Hydroxyl is of particular interest. The preferred meanings given above for R ₆ and R ₆ ' apply also to Ri, R ₂ , R3, R3', R ₄ , R5, R7, R ₈ , Rg, Rg', R10 and Rn, but these radicals may additionally be hydrogen.

Particular preference for R ₃ ' and R ₆ ' in formula (2) is given to hydrogen, N-mono- or N,N-di- Ci-C ₄ alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, or a group

_V1- ^CH ₂ CH ₂ OH _V1+ ^CH ₂ CH ₂ OH

— N N- — NCH ₂ CH ₂ N(CH ₃ ) ₃ ; — NCH ₂ CH ₂ N(CH ₃ ) ₂

CH, — N N.

CH ₂ CH ₂ OH

CH, CH,

-NHCH ₂ CH ₂ N(CH ₃ ) _{3 ;} -NHCH ₂ CH ₂ N(CH ₃ ) _{2 ;} -N[CH ₂ CH ₂ N(CH ₃ ) ₃ ] ₂ -N[CH ₂ CH ₂ N(CH ₃ ) '2J2

-N[CH ₂ CH ₂ CH ₂ N(CH ₃ ) ₂ ] ₂ and -N[CH ₂ CH ₂ CH ₂ N(CH ₃ ) '3 ^, J2.

Preferred individual compounds are the following.

The compounds mentioned above are known and for example described in WO 02/88289 und WO 04/007657. They can be prepared according to the methods described therein. Typically the precursor of hydrogen peroxide is selected from the group consisting of peroxyacids and their salts, peroxydiphosphate, urea peroxide, metal peroxides, and the salts of perborate, persilicate, perphosphate, percarbonate and mixtures thereof.

Preferably it is selected from the group consisting of perborate, persilicate, perphosphate, percarbonate and mixtures thereof, in particular perborate and percarbonate.

The most suitable peroxygen compound for this invention is hydrogen peroxide.

The carboxylic acid anhydride can be of linear structure or cyclic structure which may be aromatic, unsaturated or saturated.

For example the carboxylic acid anhydride is of formula (A), (B), (C) or (D)

wherein n is a number from 0 to 4;

Rioi and R ₁ 0 ₂ independently are hydrogen, CrCi ₈ alkyl, C ₃ -Ci ₈ alkenyl, C ₃ -Ci ₈ alkinyl or phenyl, which is unsubstututed or substituted by Ci-C ₄ alkyl, d-C ₄ alkoxy, halogen, OH or NH ₂ ; R ₁ 03 is Ci-Ci ₈ alkyl, C ₃ -Ci ₈ alkenyl, C ₃ -C ₁₈ alkinyl, NO ₂ , OH, halogen, CN, NHR _10I or NR _1O iRio ₂ ; Rio ₄ and R ₁₀₅ independently are hydrogen, Ci-Ci ₈ alkyl, C ₃ -Ci ₈ alkenyl, C ₃ -Ci ₈ alkinyl or phenyl which is unsubstututed or substituted by CrC ₄ alkyl, Ci-C ₄ alkoxy, halogen, OH or NH ₂ or R ₁₀₄ and R- _I 05 form together with the carbon atoms to which they are bonded a 5, 6 or 7- membered ring.

Specific suitable carboxylic acid anhydrides are acetic acid anhydride, phthalic acid anhydride, succinic acid anhydride, maleic acid anhydride and capronic acid anhydride.

The amounts of the individual components in the aqueous liquor are, for example, b1 ) from 0.1 to 500 mM per liter of H ₂ O ₂ or a precursor of H ₂ O ₂ , preferably from 0.5 mM to 20OmM; b2) from 0.1 to 500 mM per liter of carboxylic acid anhydride, preferably from 0.2 mM to 200 mM; c) from 0.1 μM to 500 μM per liter of the metal complex of formula (1 ), preferably from 0.25 μM to 100 μM.

The molar ratio of H ₂ O ₂ or a precursor of H ₂ O ₂ to carboxylic anhydride is, for instance, from 1 :10 to 10:1.

The molar ratio of H ₂ O ₂ or a precursor of H ₂ O ₂ to the metal complex of formula (1 ) is, for example, from 10 000:1 to 100:1.

A further aspect of the invention is a composition comprising a) a carboxylic acid anhydride and hydrogen peroxide or the precursor of hydrogen peroxide; and b) a metal complex of formula (1 )

[L _n Me _m Xp]Υ _q (1 ),

wherein Me is manganese, titanium, iron, cobalt, nickel or copper,

X is a coordinating or bridging radical, n and m are each independently of the other an integer having a value of from 1 to 8, p is an integer having a value of from 0 to 32, z is the charge of the metal complex,

Y is a counter-ion, q = z/(charge Y), and L is a ligand of formula (2)

wherein Ri _> R2, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , Rs, Rg, R10 and Rn are each independently of the others hydrogen; unsubstituted or substituted Ci-Ci ₈ alkyl or aryl; cyano; halogen; nitro; - COOR ₁₂ or -SO3R ₁₂ wherein R ₁₂ is in each case hydrogen, a cation or unsubstituted or substituted Ci-Ci ₈ alkyl or aryl; -SRi ₃ , -SO ₂ Ri ₃ or -ORi ₃ wherein Ri ₃ is in each case hydrogen or unsubstituted or substituted Ci-Ci ₈ alkyl or aryl; -NRi ₄ Ri ₅ ;

-(Ci-C ₆ alkylene)-NRi ₄ Ri ₅ ; -N ⁰ Ri ₄ Ri ₅ Ri ₆ ; -(Ci-C ₆ alkylene)-N ^Θ Ri ₄ Ri ₅ Ri ₆ ; -N(Ri ₃ )-(Ci- C ₆ alkylene)-NRi ₄ Ri ₅ ; -N[(CrC ₆ alkylene)-NRi ₄ Ri ₅ ] ₂ ; -N(Ri ₃ )-(C _r C ₆ alkylene)-

N ^Θ Ri ₄ Ri ₅ Ri6, -N[(Ci-C ₆ alkylene)-N ^Θ Ri ₄ Ri ₅ Ri ₆ ] ₂ ; -N(Ri ₃ )-N-Ri ₄ Ri ₅ or -N(Ri ₃ )- N ^Θ Ri ₄ Ri ₅ Ri6, wherein Ri ₃ is as defined above and Ri ₄ , Ri ₅ and Ri ₆ are each independ- ently of the other(s) hydrogen or unsubstituted or substituted CrCisalkyl or aryl, or Ri ₄ and Ri ₅ together with the nitrogen atom bonding them form an unsubstituted or substituted 5-, 6- or 7-membered ring which may optionally contain further heteroatoms; or Ri, R2, R3, R ₄ , Rs, Re, R ₇ , Rs, R9, R10 and Rn are each independently of the others a group _ _{N NH} . _ _{N N} _ _CH2CH2θH . __ _{N N} _ _C H ₃ . — N N ^* _Ch| ³ ;

, .CH ₂ CH ₂ OH ₊ ,CH ₂ CH ₂ OH

— N N- or — N CH, ' ^"" CH ₂ CH ₂ OH

It should be emphasised that the use of metal complex compounds together with carboxylic acid anhydrides, for example, in the bleaching of textile material, does not cause any appreciable damage to fibres and dyeings.

Processes for bleaching stains in a washing liquor are usually carried out by adding to the washing liquor which comprises H ₂ O ₂ or a precursor of H ₂ O ₂ one or more metal complex compounds of formula (1 ). Alternatively, it is possible to add a detergent that already comprises one or more metal complex compounds. It will be understood that in such an application, as well as in the other applications, the metal complex compounds of formula (1 ) can alternatively be formed in situ, the metal salt (e.g. manganese(ll) salt, such as manganese(ll) chloride, and/or iron(ll) salt, such as iron(ll) chloride) and the ligand being added in the desired molar ratios. The present invention relates also to a detergent, cleaning, disinfecting or bleaching composition containing

I) from 0 to 50 wt-%, preferably from 0 to 30 wt-% of at least one anionic surfactant (A) and/or of a non-ionic surfactant (B), II) from 0 to 70 wt-%, preferably from 0 to 50 wt-% of at least one builder substance (C),

III) 1 - 99 wt-%, preferably 1 - 50 wt-%, of hydrogen peroxide and/or at least a precursor of hydrogen peroxide,

IV) at least one metal complex compound (D) of formula (1 ) as defined above in an amount that, in the liquor, gives a concentration of from 0.1 to 100 mg/litre of liquor, preferably from 0.2 to 50 mg/litre of liquor, when from 0.5 to 20 g/litre of the detergent, cleaning, disinfecting or bleaching agent are added to the liquor, (V) 0.5 - 50 wt-% of at least one carboxylic acid anhydride (E) and

V) water ad 100 wt-%, wherein the percentages are in each case percentages by weight, based on the total weight of the composition.

The above percentages are in each case percentages by weight, based on the total weight of the composition. The compositions preferably contain from 0.001 to 2 wt-% of at least one metal complex compound of formula (1 ), especially from 0.001 to 1 wt-% and preferably from 0.02 to 1 wt-%.

When the compositions according to the invention comprise a component A) and/or B), the amount thereof is preferably from 1 to 50 wt-%, especially from 1 to 30 wt-%.

When the compositions according to the invention comprise a component C), the amount thereof is preferably from 1 to 70 wt-%, especially from 1 to 50 wt-%. Special preference is given to an amount of from 5 to 50 wt-% and especially an amount of from 10 to 50 wt-%.

The composition according to the invention can be, for example, a bleach containing detergent, a heavy-duty detergent or a separate bleaching additive, or a stain remover that is to be applied directly. A bleaching additive is used for removing coloured stains on textiles in a separate liquor before the clothes are washed with a bleach-free detergent. A bleaching additive can also be used in a liquor together with a bleach-free detergent. Stain removers can be applied directly to the textile in question and are used especially for pretreatment in the event of heavy local soiling. The stain remover can be applied in liquid form, by a spraying method or in the form of a solid substance.

A specific embodiment of the invention is a solid formulation containing a) from 0.2 to 99 wt-%, preferably from 0.2 to 40 wt-%, especially from 0.2 to 30 wt-%, of at least one metal complex compound of formula (1 ) as defined above and 1 - 50 wt-%, of hydrogen peroxide and/or at least a precursor of hydrogen peroxide and 1 - 50 wt-%, of a carboxylic acid anhydride, b) from 1 to 99 wt-%, preferably from 10 to 99 wt-%, especially from 20 to 80 wt-%, of at least one binder, c) from 0 to 20 wt-%, especially from 1 to 20 wt-%, of at least one encapsulating material, d) from 0 to 20 wt-% of at least one further additive and e) from 0 to 20 wt-% water.

Preferably the solid formulation is in the form of granules.

Granules can be prepared in known manner, for example, by first preparing an initial powder by spray-drying an aqueous suspension comprising all the components listed above except for the transition metal complex compound and then adding the dry transition metal complex compound and mixing everything together. It is also possible to add the complexcompound to an aqueous suspension containing all other components and then to carry out spray- drying.

The anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof. Preference is given to alkylbenzenesulfonat.es, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to an α- sulfonic fatty acid salt or an ester thereof.

Preferred sulfonates are, for example, alkylbenzenesulfonat.es having from 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical, alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical, and fatty acid salts derived from palm oil or tallow and having from 8 to 18 carbon atoms in the alkyl moiety. The average molar number of ethylene oxide units added to the alkyl ether sulfates is from 1 to 20, preferably from 1 to 10. The cation in the anionic surfactants is preferably an alkaline metal cation, especially sodium or potassium, more especially sodium. Preferred carboxylates are alkali metal sarcosinates of formula R ₄₄ -CON(R ₄₅ )CH ₂ COOM ₁ wherein R ₄₄ is C ₉ -Ci ₇ alkyl or C ₉ -Ci ₇ alkenyl, R ₄₅ is Ci-C ₄ alkyl and M ₁ is an alkali metal, especially sodium.

The non-ionic surfactant may be, for example, a primary or secondary alcohol ethoxylate, especially a Cs-C ₂ O aliphatic alcohol ethoxylated with an average of from 1 to 20 mol of ethylene oxide per alcohol group. Preference is given to primary and secondary C ₁₀ -C ₁₅ aliphatic alcohols ethoxylated with an average of from 1 to 10 mol of ethylene oxide per alcohol group. Non-ethoxylated non-ionic surfactants, for example alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamide), may likewise be used.

The total amount of anionic and non-ionic surfactants is preferably from 1 to 50 wt-%, especially from 5 to 40 wt-% and more especially from 5 to 30 wt-%. The lower limit of those surfactants to which even greater preference is given is 10 wt-%.

As builder substance C) there come into consideration, for example, alkali metal phosphates, especially tripolyphosphates, carbonates and hydrogen carbonates, especially their sodium salts, silicates, aluminum silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) and mixtures of such compounds.

Silicates that are especially suitable are sodium salts of crystalline layered silicates of the formula NaHSitO ₂ t ₊₁ .pH ₂ O or Na ₂ Si _t O ₂ t ₊₁ .pH ₂ O wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.

Among the aluminum silicates, preference is given to those commercially available under the names zeolite A, B, X and HS, and also to mixtures comprising two or more such components. Special preference is given to zeolite A.

Among the polycarboxylates, preference is given to polyhydroxycarboxylat.es, especially citrates, and acrylates, and also to copolymers thereof with maleic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylene- diamine disuccinate either in racemic form or in the enantiomerically pure (S, S) form. Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1 ,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta- methylenephosphonic acid, and also salts thereof. As binder (b) for the granules there come into consideration water-soluble, dispersible or water-emulsifiable anionic dispersants, non-ionic dispersants, polymers and waxes.

The anionic dispersants used are, for example, commercially available water-soluble anionic dispersants for dyes, pigments etc.

The following products, especially, come into consideration: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenyls or diphenyl oxides and optionally formaldehyde, (mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalenesulfonic acids, sodium salts of polymerised alkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkyl polyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acid, sodium salts of alkyl diglycol ether sulfates, sodium salts of polynaphthalenemethane- sulfonates, lignosulfonates or oxylignosulfonates and heterocyclic polysulfonic acids.

Especially suitable anionic dispersants are condensation products of naphthalenesulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, (mono-/di-)- alkylnaphthalenesulfonat.es, polyalkylated polynuclear arylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid, lignosulfonates, oxylignosulfonates and condensation products of naphthalenesulfonic acid with a polychloromethyldiphenyl.

Suitable non-ionic dispersants are especially compounds having a melting point of, preferably, at least 35°C that are emulsifiable, dispersible or soluble in water, for example the following compounds:

1. fatty alcohols having from 8 to 22 carbon atoms, especially cetyl alcohol;

2. addition products of, preferably, from 2 to 80 mol of alkylene oxide, especially ethylene oxide, wherein some of the ethylene oxide units may have been replaced by substituted epoxides, such as styrene oxide and/or propylene oxide, with higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty amides having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl phenols, benzyl phenols or alkyl phenols, the alkyl radicals of which have at least 4 carbon atoms;

3. alkylene oxide, especially propylene oxide, condensation products (block polymers); 4. ethylene oxide/propylene oxide adducts with diamines, especially ethylenediamine;

5. reaction products of a fatty acid having from 8 to 22 carbon atoms and a primary or secondary amine having at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or alkylene oxide addition products of such hydroxyalkyl-group-containing reaction products; 6. sorbitan esters, preferably having long-chain ester groups, or ethoxylated sorbitan esters, such as polyoxyethylene sorbitan monolaurate having from 4 to 10 ethylene oxide units or polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene oxide units; 7. addition products of propylene oxide with a tri- to hexa-hydric aliphatic alcohol having from

3 to 6 carbon atoms, e.g. glycerol or pentaerythritol; and 8. fatty alcohol polyglycol mixed ethers, especially addition products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol of propylene oxide with aliphatic monoalcohols having from 8 to 22 carbon atoms.

The compositions may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the classes bis-triazinylamino- stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis- benzofuranylbiphenyl, α bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarin derivative or a pyrazoline derivative.

The compositions may furthermore comprise one or more auxiliaries. Such auxiliaries are, for example, dirt-suspending agents, for example sodium carboxymethylcellulose; pH regulators, for example alkali metal or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and the granulating properties, for example sodium sulfate; perfumes; and also, if appropriate, antistatics and softening agents such as, for example, smectite; bleaching agents; pigments; and/or toning agents. These constituents should especially be stable to any bleaching agent employed. Such auxiliaries are added in a total amount of from 0.1 to 20 wt-%, preferably from 0.5 to 10 wt-%, especially from 0.5 to 5 wt-%, based on the total weight of the detergent formulation. Furthermore, the detergent may optionally also comprise enzymes. Enzymes can be added for the purpose of stain removal. The enzymes usually improve the action on stains caused by protein or starch, such as, for example, blood, milk, grass or fruit juices. Preferred enzymes are amylases and proteases, especially proteases. Other preferred enzymes include lipases, cellulases and mannanases.

Amylases: The present invention preferably makes use of amylases having improved stability in detergents, especially improved oxidative stability. Such amylases are non-limitingly illustrated by the following: (a) An amylase according to WO 94/02597, Novo Nordisk A/S as further illustrated by a mutant in which substitution is made, using alanine or threonine (preferably threonine), of the methionine residue located in position 197 of the B.licheniformis alpha-amylase, known as TE RM AM YL ^® , or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B.subtilis, or B.stearothermophilus; (b) Stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant α-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B. licheniformis NCIB8061. Other commercially available detergent amylases, such as Duramyl ^® , Stainzyme ^® , Natalase ^® , Ban ^® and Fungamyl ^® , are sold e.g. by NOVOZYMES A/S. Any other oxidative stability-enhanced amylase can be used.

Proteases: Protease enzymes are usually present in preferred embodiments of the invention at levels between 0.001 wt-% and 5 wt-%. The proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Suitable commercial proteolytic enzymes include Alcalase ^® , Esperase ^® , Everlase ^® , Durazyme ^® , Savinase ^® , Maxatase ^® , Kannase ^® , Maxacal ^® , and

Maxapem ^® 15 (protein engineered Maxacal). Purafect ^® and subtilising BPN and BPN' are also commercially available. Lipase: Lipases work on greasy soil and stains. When present, lipases comprise from about 0.001 wt-% to about 5 wt-% of the detergent or cleaning formulation. Suitable lipases for use herein include those of bacterial, animal and fungal origin, including those from chemically or genetically modified mutants. Commercially available detergent lipases, such as Lipolase ^® , Lipolase Ultra ^® and Lipoprime ^® , are sold e.g. by NOVOZYMES A/S.

When incorporating lipases into the instant compositions, their stability and effectiveness may in certain instances be enhanced by combining them with small amounts (e.g., less than 0.5 wt-% of the composition) of oily but non-hydrolyzing materials.

Cellulases: Cellulases are enzymes that react with cellulose and its derivatives and hydrolyse them to form glucose, cellobiose and cellooligosaccharides. Cellulases remove dirt and, in addition, have the effect of enhancing the soft handle of the fabric and reduce graying. Commercially available cellulases, such as Celluzyme ^® , Careuyme ^® and Endolase ^® are, are sold e.g. by NOVOZYMES A/V.

The enzymes, when used, may be present in a total amount of from 0.01 to 5% by weight, especially from 0.05 to 5 wt-% and more especially from 0.1 to 4 wt-%, based on the total weight of the detergent formulation.

In order to enhance the bleaching action, the compositions may, in addition to the catalysts described herein, also comprise photocatalysts the action of which is based on the generation of singlet oxygen.

Further preferred additives to the compositions according to the invention are dye-fixing agents and/or polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions. Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine-N-oxides, which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range of from 5000 to 60 000, more especially from 10 000 to 50 000. Such polymers are usually used in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5 wt-%, more especially from 0.1 to 2 wt-%, based on the total weight of the detergent formulation. Preferred polymers are those mentioned in WO-A-02/02865 (see especially page 1 , last paragraph and page 2, first paragraph). The detergent formulations can take a variety of physical forms such as, for example, powder granules, tablets (tabs) and liquid. Examples thereof include, inter alia, conventional high- performance detergent powders, supercompact high-performance detergent powders and tabs. One important physical form is the so-called concentrated granular form, which is added to a washing machine.

Also of importance are so-called compact or supercompact detergents. In the field of detergent manufacture, there is a trend towards the production of such detergents that contain an increased amount of active substances. In order to minimize energy consumption during the washing procedure, compact or supercompact detergents need to act effectively at low washing temperatures, for example below 40 ⁰ C, or even at room temperature (25°C). Such detergents usually contain only small amounts of fillers or of substances, such as sodium sulfate or sodium chloride, required for detergent manufacture. The total amount of such substances is usually from 0 to 10 wt-%, especially from 0 to 5 wt-%, more especially from 0 to 1 wt-%, based on the total weight of the detergent formulation. Such (super)compact detergents usually have a bulk density of from 650 to 1000 g/l, especially from 700 to 1000 g/l and more especially from 750 to 1000 g/l.

The detergent formulations can also be in the form of tablets (tabs). The advantages of tabs reside in the ease of dispensing and convenience in handling. Tabs are the most compact form of solid detergent formulation and usually have a volumetric density of, for example, from 0.9 to 1.3 kg/litre. To achieve rapid dissolution, such tabs generally contain special dissolution aids: - carbonate/hydrogen carbonate/citric acid as effervescents;

- disintegrators, such as cellulose, carboxymethyl cellulose or cross-linked polyvinylpyrrolidone);

- rapidly dissolving materials, such as sodium (potassium) acetates, or sodium (potassium) citrates; - rapidly dissolving, water-soluble, rigid coating agents, such as dicarboxylic acids. The tabs may also comprise combinations of such dissolution aids.

The detergent formulation may also be in the form of an aqueous liquid containing from 5 to 50 wt-%, preferably from 10 to 35 wt-%, of water or in the form of a non-aqueous liquid containing no more than 5 wt-%, preferably from 0 to 1 wt-%, of water. Non-aqueous liquid detergent formulations may comprise other solvents as carriers. Low molecular weight primary or secondary alcohols, for example methanol, ethanol, propanol and isopropanol, are suitable for that purpose. The solubilising surfactant used is preferably a monohydroxy alcohol but polyols, such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerol and 1 ,2-propanediol) can also be used. Such carriers are usually used in a total amount of from 5% to 90% by weight, preferably from 10 wt-% to 50 wt-%, based on the total weight of the detergent formulation. The detergent formulations can also be used in so-called "unit liquid dose" form.

Yet another aspect of the invention is the use of a composition as described above optionally with a surfactant and further adjuvants as bleaching formulation for textile materials, pulp and paper and waste water.

The definitions and preferences outlined above for the process, apply equally to the other aspects of the invention.

The following examples illustrate the invention.

Example 1 : succinic acid anhydrdide at 40 ⁰ C

0.8 g BC01 tea stained fabric, 0.8 g BC02 coffee stained fabric (100% cotton) and 28.4g 100% white unstained cotton are washed for 1 hour at 40° C with 150 ml washing liquor containing 8g/l of a commercial liquid detergent.

Bleach System:

1 ) 3mM H ₂ O ₂ comparative

2) 3mM H ₂ O ₂ + 1 μM L1 comparative

3) 3mM H ₂ O ₂ + 1 μM L1 + 2mM Succinic acid anhydride inventive 4) 3mM H2O ₂ + I mM TAED comparative

Brightness (Y) of the tea and coffee stained fabric is spectrophotometrically measured before and after the washing cycle (Spektraflash 500 Remissionspektrophotometer). The difference between both measurements is presented in Table 1. A greater difference is indicative for a better bleach result. Table 1

The inventive example results in a clearly improved result.

Example 2: different anhydrides at 40 ⁰ C

0.8 g BC01 tea stained fabric (100% cotton) and 30 g 100% white unstained cotton are washed for 1 hour at 40° C with 150 ml washing liquor containing 5 g/l IEC456 standard detergent from WfK. The pH is adjusted with 1 M H ₂ SO ₄ in such a way that a pH of 9.8 to 10.0 results after the washing cycle.

Bleach System:

1 ) 6.5mM H ₂ O ₂ comparative

2) 6.5mM H ₂ O ₂ + 2mM Bernsteinsaureanhydrid comparative

3) 6.5mM H ₂ O ₂ + 2mM Maleinsaureanhydrid comparative 4) 6.5mM H ₂ O ₂ + 2mM Phthalsaureanhydrid comparative

5) 3mM H ₂ O ₂ + 1.5μM L1 comparative

6) 3mM HO ₂ + 1.5μM L1 + 2mM succinic acid anhydride inventive

7) 3mM H ₂ O ₂ + 1.5μM L1 + 2mM maleic acid anhydride inventive

8) 3mM H ₂ O ₂ + 1.5μM L1 + 2mM phthalic acid anhydride inventive Brightness (Y) of the tea stained fabric is spectrophotometrically measured before and after the washing cycle (Spektraflash 500 Remissionspektrophotometer). The difference between both measurements is presented in Table 2. A greater difference is indicative for a better bleach result. Table 2

The bleach results of the inventive examples are significantly better than those of the comparative examples.

Example 3: succinic acid anhydride and maleic acid anhydride at 30° C and various pH values

0.8 g BC01 tea stained fabric (100% cotton) and 30 g 100% white unstained cotton are washed for 1 hour at 30° C with 150 ml washing liquor containing 5 g/l IEC456 standard detergent from WfK. The pH is adjusted with 1 M H ₂ SO ₄ in such a way that a pH of 8.0 to 10.0 results after the washing cycle. Peroxide concentration is 3mM, the Mn complex L1 is 1.5μM. Brightness is measured as indicated above. The results are presented in Table 3 Table 3

A bleach maximum is reached at a pH of about 9 for both anhydrides.

Example 4: linear anhydrides

0.8 g BC01 tea stained fabric (100% cotton) and 30 g 100% white unstained cotton are washed for 1 hour at 30° C with 150 ml washing liquor containing 8 g/l liquid AATCC standard detergent from AATCC. The pH is adjusted with 1 M H ₂ SO ₄ in such a way that a pH of 9.2 results after the washing cycle. Peroxide concentration is 3mM, the Mn complex L1 is 1.5μM. Brightness is measured as indicated above. The results are presented in Table 4. Table 4

The inventive examples show significantly improved bleach results.

Example 5: bleaching of raw cotton fabric

10g unbleached cotton are bleached at 40° C for 1 hour in 150ml liquor containing 20OmM carbonate buffer (pH 9.3), 1 g/l Neodol 45 7EO and 50μM Diethylentriamin-penta- (methylenphosphonsaure) (Dequest 2066). Peroxide and Mn comlex L1 are added as indicated in Table 5. Brightness is measured as indicated above. The results are presented in Table 5. Table 5